2,17-Dichloro-8,9,10,11-tetra-hydro-19H-dibenzo[k,n][1,10,4,7]dioxadiaza-cyclo-penta-decine-7,12(6H,13H)-dione.

In the crystal structure of the title compound, C(19)H(18)Cl(2)N(2)O(4), N-H⋯O hydrogen bonds link the mol-ecules into infinite chains along the b axis. The structure also features weak C-H⋯O and C-H⋯Cl hydrogen bonds and C-H⋯π and (lone pair)⋯π inter-actions [Cl⋯centroid = 3.5871 (7) Å]. An intra-molecular N-H⋯O bond occurs.

Related literature

For the synthesis, see: Ertul et al. (2009 ▶). For applications of macrocycles, see: Hayvali & Hayvali (2005 ▶); Kleinpeter et al. (1997 ▶); Jaiyu et al. (2007 ▶); Christensen et al. (1997 ▶); Alexander (1995 ▶).

Experimental

Crystal data

C19H18Cl2N2O4

M = 409.25

Monoclinic,

a = 12.0877 (3) Å

b = 8.73462 (15) Å

c = 17.3712 (4) Å

β = 93.588 (2)°

V = 1830.48 (7) Å3

Z = 4

Cu Kα radiation

μ = 3.44 mm−1

T = 120 K

0.31 × 0.22 × 0.21 mm

Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer

Absorption correction: analytical (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.175, T max = 0.342

19596 measured reflections

3271 independent reflections

3210 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.074

S = 1.07

3271 reflections

244 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.29 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812020351/aa2058sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020351/aa2058Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C19H18Cl2N2O4	F(000) = 848
Mr = 409.25	Dx = 1.484 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ybc	Cell parameters from 16650 reflections
a = 12.0877 (3) Å	θ = 3.7–67.1°
b = 8.73462 (15) Å	µ = 3.44 mm−1
c = 17.3712 (4) Å	T = 120 K
β = 93.588 (2)°	Prism, colourless
V = 1830.48 (7) Å3	0.31 × 0.22 × 0.21 mm
Z = 4

Agilent Xcalibur Atlas Gemini ultra diffractometer	3271 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	3210 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.028
Detector resolution: 10.3784 pixels mm-1	θmax = 67.1°, θmin = 3.7°
Rotation method data acquisition using ω scans	h = −14→14
Absorption correction: analytical (CrysAlis PRO; Agilent, 2010)	k = −8→10
Tmin = 0.175, Tmax = 0.342	l = −20→20
19596 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0376P)2 + 0.7612P] where P = (Fo2 + 2Fc2)/3
3271 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.20 e Å−3
2 restraints	Δρmin = −0.29 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The distance between hydrogen atoms and nitrogen atoms was restrained. The bond length was set to 0.87 Å with σ 0.02. The isotropic temperature parameters of hydrogen atoms were calculated as 1.2*Ueq of the parent atom.

	x	y	z	Uiso*/Ueq
Cl1	0.86335 (3)	1.01411 (4)	0.16078 (2)	0.03147 (11)
Cl2	1.00225 (3)	0.24819 (5)	−0.01843 (2)	0.03989 (12)
O4	0.78538 (8)	0.52610 (11)	0.38371 (5)	0.0251 (2)
O1	0.64125 (7)	0.49162 (11)	0.15585 (5)	0.0248 (2)
O3	0.58083 (8)	0.72265 (11)	0.47012 (6)	0.0306 (2)
O2	0.39104 (8)	0.69986 (11)	0.15386 (6)	0.0291 (2)
N2	0.55581 (9)	0.49941 (13)	0.40482 (6)	0.0247 (2)
H1N2	0.5904	0.4132	0.3923	0.030*
C19	0.74034 (11)	0.56132 (16)	0.45584 (8)	0.0262 (3)
H19A	0.7809	0.6463	0.4799	0.031*
H19B	0.7490	0.4736	0.4899	0.031*
C3	0.79942 (11)	0.91308 (16)	0.29832 (8)	0.0269 (3)
H3	0.7880	1.0154	0.3102	0.032*
C5	0.84978 (11)	0.71987 (16)	0.20783 (8)	0.0241 (3)
H5	0.8732	0.6951	0.1594	0.029*
C11	0.79350 (12)	0.34870 (16)	−0.00686 (8)	0.0276 (3)
H11	0.7834	0.3274	−0.0593	0.033*
C8	0.82559 (11)	0.40890 (14)	0.15178 (8)	0.0222 (3)
C1	0.79727 (10)	0.64599 (15)	0.33323 (8)	0.0230 (3)
C6	0.82934 (10)	0.60427 (15)	0.25987 (8)	0.0223 (3)
C7	0.83966 (11)	0.43695 (15)	0.23779 (8)	0.0237 (3)
H7A	0.9119	0.3998	0.2567	0.028*
H7B	0.7842	0.3784	0.2631	0.028*
C13	0.72294 (11)	0.43609 (15)	0.11165 (8)	0.0228 (3)
C9	0.91159 (11)	0.35413 (15)	0.11042 (8)	0.0248 (3)
H9	0.9809	0.3374	0.1352	0.030*
C12	0.70686 (11)	0.40584 (16)	0.03341 (8)	0.0268 (3)
H12	0.6381	0.4238	0.0079	0.032*
N1	0.49166 (10)	0.57462 (14)	0.24811 (7)	0.0271 (3)
H1N1	0.5560	0.5268	0.2600	0.033*
C15	0.46922 (10)	0.61525 (15)	0.17506 (8)	0.0230 (3)
C14	0.54225 (11)	0.54793 (16)	0.11649 (8)	0.0242 (3)
H14A	0.5038	0.4652	0.0889	0.029*
H14B	0.5604	0.6256	0.0794	0.029*
C18	0.61793 (11)	0.60295 (15)	0.44482 (7)	0.0242 (3)
C2	0.78030 (11)	0.79873 (16)	0.35175 (8)	0.0263 (3)
H2	0.7562	0.8245	0.3999	0.032*
C4	0.83550 (11)	0.87211 (16)	0.22751 (8)	0.0250 (3)
C17	0.44063 (11)	0.52947 (16)	0.38020 (8)	0.0270 (3)
H17A	0.4034	0.5749	0.4225	0.032*
H17B	0.4038	0.4337	0.3666	0.032*
C10	0.89470 (11)	0.32410 (16)	0.03211 (8)	0.0268 (3)
C16	0.43191 (11)	0.63655 (16)	0.31133 (8)	0.0276 (3)
H16A	0.3546	0.6506	0.2945	0.033*
H16B	0.4624	0.7357	0.3262	0.033*

	U11	U22	U33	U12	U13	U23
Cl1	0.0375 (2)	0.02398 (18)	0.0333 (2)	−0.00168 (13)	0.00512 (14)	0.00670 (13)
Cl2	0.0333 (2)	0.0531 (2)	0.0343 (2)	0.01109 (16)	0.00956 (15)	−0.00592 (16)
O4	0.0283 (5)	0.0241 (5)	0.0232 (5)	0.0001 (4)	0.0043 (4)	0.0026 (4)
O1	0.0209 (5)	0.0307 (5)	0.0227 (5)	0.0044 (4)	0.0010 (4)	0.0008 (4)
O3	0.0355 (5)	0.0277 (5)	0.0291 (5)	0.0002 (4)	0.0056 (4)	−0.0042 (4)
O2	0.0259 (5)	0.0293 (5)	0.0323 (5)	0.0061 (4)	0.0027 (4)	0.0076 (4)
N2	0.0253 (6)	0.0234 (6)	0.0255 (6)	0.0011 (4)	0.0013 (5)	0.0001 (4)
C19	0.0294 (7)	0.0287 (7)	0.0205 (6)	−0.0023 (6)	0.0020 (5)	0.0012 (5)
C3	0.0283 (7)	0.0210 (7)	0.0313 (7)	0.0004 (5)	0.0005 (5)	−0.0014 (5)
C5	0.0233 (6)	0.0260 (7)	0.0232 (6)	−0.0011 (5)	0.0025 (5)	0.0002 (5)
C11	0.0333 (7)	0.0268 (7)	0.0227 (7)	0.0004 (6)	0.0034 (5)	0.0003 (5)
C8	0.0246 (6)	0.0161 (6)	0.0258 (7)	−0.0012 (5)	0.0014 (5)	0.0019 (5)
C1	0.0198 (6)	0.0244 (7)	0.0245 (6)	−0.0019 (5)	−0.0006 (5)	0.0030 (5)
C6	0.0181 (6)	0.0226 (6)	0.0259 (7)	−0.0004 (5)	−0.0008 (5)	0.0004 (5)
C7	0.0239 (6)	0.0224 (6)	0.0248 (7)	0.0012 (5)	0.0004 (5)	0.0013 (5)
C13	0.0235 (6)	0.0201 (6)	0.0251 (7)	0.0004 (5)	0.0041 (5)	0.0011 (5)
C9	0.0231 (6)	0.0213 (6)	0.0299 (7)	−0.0002 (5)	0.0015 (5)	0.0019 (5)
C12	0.0257 (7)	0.0284 (7)	0.0261 (7)	0.0022 (5)	−0.0001 (5)	0.0016 (5)
N1	0.0258 (6)	0.0309 (6)	0.0247 (6)	0.0087 (5)	0.0016 (4)	0.0007 (5)
C15	0.0211 (6)	0.0195 (6)	0.0283 (7)	−0.0029 (5)	0.0007 (5)	0.0018 (5)
C14	0.0222 (6)	0.0256 (7)	0.0244 (7)	0.0016 (5)	−0.0008 (5)	0.0036 (5)
C18	0.0301 (7)	0.0246 (7)	0.0183 (6)	−0.0015 (5)	0.0042 (5)	0.0030 (5)
C2	0.0267 (7)	0.0278 (7)	0.0248 (7)	0.0005 (5)	0.0034 (5)	−0.0028 (6)
C4	0.0240 (6)	0.0231 (7)	0.0278 (7)	−0.0014 (5)	0.0001 (5)	0.0045 (5)
C17	0.0244 (7)	0.0300 (7)	0.0268 (7)	−0.0005 (5)	0.0031 (5)	0.0003 (6)
C10	0.0279 (7)	0.0237 (7)	0.0295 (7)	0.0020 (5)	0.0082 (5)	0.0001 (5)
C16	0.0277 (7)	0.0292 (7)	0.0262 (7)	0.0057 (6)	0.0030 (5)	−0.0006 (6)

Cl1—C4	1.7451 (14)	C8—C13	1.4050 (18)
Cl2—C10	1.7448 (14)	C8—C7	1.5132 (18)
O4—C1	1.3794 (16)	C1—C2	1.391 (2)
O4—C19	1.4306 (16)	C1—C6	1.4031 (19)
O1—C13	1.3766 (16)	C6—C7	1.5185 (19)
O1—C14	1.4282 (15)	C7—H7A	0.9700
O3—C18	1.2300 (17)	C7—H7B	0.9700
O2—C15	1.2377 (16)	C13—C12	1.3864 (19)
N2—C18	1.3417 (18)	C9—C10	1.388 (2)
N2—C17	1.4548 (17)	C9—H9	0.9300
N2—H1N2	0.8948	C12—H12	0.9300
C19—C18	1.5243 (19)	N1—C15	1.3292 (18)
C19—H19A	0.9700	N1—C16	1.4560 (18)
C19—H19B	0.9700	N1—H1N1	0.8962
C3—C4	1.378 (2)	C15—C14	1.5077 (19)
C3—C2	1.393 (2)	C14—H14A	0.9700
C3—H3	0.9300	C14—H14B	0.9700
C5—C6	1.3880 (19)	C2—H2	0.9300
C5—C4	1.387 (2)	C17—C16	1.5171 (19)
C5—H5	0.9300	C17—H17A	0.9700
C11—C10	1.377 (2)	C17—H17B	0.9700
C11—C12	1.388 (2)	C16—H16A	0.9700
C11—H11	0.9300	C16—H16B	0.9700
C8—C9	1.3856 (19)
C1—O4—C19	117.00 (10)	C10—C9—H9	119.9
C13—O1—C14	117.60 (10)	C13—C12—C11	119.91 (13)
C18—N2—C17	121.67 (12)	C13—C12—H12	120.0
C18—N2—H1N2	116.0	C11—C12—H12	120.0
C17—N2—H1N2	122.3	C15—N1—C16	122.65 (11)
O4—C19—C18	111.17 (10)	C15—N1—H1N1	117.8
O4—C19—H19A	109.4	C16—N1—H1N1	117.7
C18—C19—H19A	109.4	O2—C15—N1	123.36 (12)
O4—C19—H19B	109.4	O2—C15—C14	120.06 (12)
C18—C19—H19B	109.4	N1—C15—C14	116.55 (11)
H19A—C19—H19B	108.0	O1—C14—C15	108.66 (10)
C4—C3—C2	118.92 (13)	O1—C14—H14A	110.0
C4—C3—H3	120.5	C15—C14—H14A	110.0
C2—C3—H3	120.5	O1—C14—H14B	110.0
C6—C5—C4	120.49 (13)	C15—C14—H14B	110.0
C6—C5—H5	119.8	H14A—C14—H14B	108.3
C4—C5—H5	119.8	O3—C18—N2	123.61 (13)
C10—C11—C12	118.92 (13)	O3—C18—C19	122.07 (12)
C10—C11—H11	120.5	N2—C18—C19	114.31 (12)
C12—C11—H11	120.5	C1—C2—C3	120.07 (13)
C9—C8—C13	118.00 (12)	C1—C2—H2	120.0
C9—C8—C7	121.76 (12)	C3—C2—H2	120.0
C13—C8—C7	120.24 (12)	C3—C4—C5	121.37 (12)
O4—C1—C2	123.97 (12)	C3—C4—Cl1	119.56 (11)
O4—C1—C6	115.20 (12)	C5—C4—Cl1	119.08 (11)
C2—C1—C6	120.83 (12)	N2—C17—C16	111.17 (11)
C5—C6—C1	118.23 (12)	N2—C17—H17A	109.4
C5—C6—C7	121.01 (12)	C16—C17—H17A	109.4
C1—C6—C7	120.75 (12)	N2—C17—H17B	109.4
C8—C7—C6	113.54 (11)	C16—C17—H17B	109.4
C8—C7—H7A	108.9	H17A—C17—H17B	108.0
C6—C7—H7A	108.9	C11—C10—C9	121.58 (13)
C8—C7—H7B	108.9	C11—C10—Cl2	118.62 (11)
C6—C7—H7B	108.9	C9—C10—Cl2	119.77 (11)
H7A—C7—H7B	107.7	N1—C16—C17	110.63 (11)
O1—C13—C12	123.54 (12)	N1—C16—H16A	109.5
O1—C13—C8	115.16 (11)	C17—C16—H16A	109.5
C12—C13—C8	121.29 (12)	N1—C16—H16B	109.5
C8—C9—C10	120.29 (12)	C17—C16—H16B	109.5
C8—C9—H9	119.9	H16A—C16—H16B	108.1

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O2i	0.89	2.05	2.8945 (15)	158
C14—H14A···O3i	0.97	2.54	3.5026 (17)	172
C14—H14B···O3ii	0.97	2.34	3.2934 (17)	167
C16—H16B···O1iii	0.97	2.59	3.2843 (17)	129
C19—H19A···Cl2iv	0.97	2.81	3.6201 (14)	142
C9—H9···Cg1v	0.93	2.88	3.8006 (14)	174
N1—H1N1···O1	0.90	2.16	2.5935 (15)	109

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O2i	0.89	2.05	2.8945 (15)	158
C14—H14A⋯O3i	0.97	2.54	3.5026 (17)	172
C14—H14B⋯O3ii	0.97	2.34	3.2934 (17)	167
C16—H16B⋯O1iii	0.97	2.59	3.2843 (17)	129
C19—H19A⋯Cl2iv	0.97	2.81	3.6201 (14)	142
C9—H9⋯Cg1v	0.93	2.88	3.8006 (14)	174
N1—H1N1⋯O1	0.90	2.16	2.5935 (15)	109

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .